Journal
COORDINATION CHEMISTRY REVIEWS
Volume 249, Issue 24, Pages 2854-2879Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2005.03.006
Keywords
lanthanides; ytterbium; chirality; paramagnetic NMR; circular dichroism; near infrared
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The determination of solution structure of small to medium size chiral lanthanide complexes through paramagnetic NMR and circular dichroism is briefly reviewed. The main focus is on ytterbium as the rare earth, because of its negligible contact contribution to the hyperfine shift and of its intense CD spectrum in the near IR. The structures discussed contain various stereogenic elements: classical chiral centres, atropisomeric axes, slowly interconverting conformations, which gives rise to a manifold of situations to be identified, classified, and characterised through spectroscopic tools. The fallout of these structural properties are in enantioselective catalysis, in molecular recognition, or even in biomedicine, on account of the role of Gd3+ complexes as MRI contrast agents. Moreover, the information encoded in the NMR and CD spectra of Ln(3+) complexes may be used to extract original data on the solution stereochemistry of organic molecules used as ligands. The first part summarises some basic theoretical aspects, with special emphasis onto those which have practical consequences in the experimental design. A discussion of selected applications can be found in the second part. (c) 2005 Elsevier B.V. All rights reserved.
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